Decachloro-3-hydroxypentacyclodecane-3-phosphonates



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DECACEHJORQ-'3-HYDROXYPENTACYCLO- DECANE-Si-PHOSPHONATES Edward D.Weill, Lewiston, and Keith J. Smith, Lockport, N.Y., assignors to HookerChemical Corporation, Niagara Falls, N.Y., a corporation of New York NDrawing. Filed July 7, 1961, Ser. No. 122,402 8 Claims. (Cl. 260-461) 701 (:1 lab be 01 01 v 0 3 (to t (Q-LOB K (9) 2 i a as 01-0 where R and Rare members selected from the group consisting of hydrogen, alkyl,substituted alkyl, aryl, substituted aryl and heterocyclic radicals,with the option that R and R when conjoined, are chosenfrom the groupconsistingof alkylene, substituted alkylene, arylene, substitutedarylene, and divalent heterocyclic radicals.

By substituted is meant substituted by halogen, alkyl, nitro, alkoxy,aryloxy, alkylmercapto, arylmercapto and alkenyl.

The group R or R may be of high molecular weight and either or both mayin fact represent macromolecular chains; the compositions of theinvention may, therefore, be macromolecular (polymeric) substances aswell as lower molecular weight substances.

Since the novel products of this invention may be considered asphosphonate derivatives of the previously described pentacyclostructure,nomenclature difliculties may ,be avoided by referring to this parentstructure (see below) as C Cl C1 or or an E fill +:CwClw hereinafter l as 0-0 (a 51 While this structure is believed correct to the best of ourpresent knowledge, what we mean to describe as our invention are thecompounds made as described herein, The generic structure written abovewill hereinafter be written in abbreviated form as C Cl (OH)PO(OR (0Rand the specific embodiments will be abbreviated in an analogousfashion. Examples of compounds of the invention include among others,the following compounds (because of the unsettled Siitiitl it 3,2d2fi92atented Aug. 24, 1965 and difficult nomenclature, the compounds arerepresented structurally rather than by names).

011 011, omommm-Po 00d 0H2 onion,

011 0112 7 C Clw(0H)PO(OOH ou O OCHz ll CmChMOIDP CH3 OCH O 0 CH CH OH OCH; CzH

0 06112 CHzO While the causes of marine fouling are presently obscure,its effect on economic and military affairs is readily apparent. It isestimated that the cost of preventing, slowing down and treating marinefouling runs into millions of dollars annually, and no satisfactorysolution is in sight. For example, the efficiency and the period of useof a pier, ship, boat, buoy or marine structure is greatly reducedunless some prophylactic treatment is followed. Ships which have becomeencrusted with marine organisms lose a substantial part of their normalspeed and mechanical efficiency. Furthermore, many ships and marinestructures such as bulkheads, buoys, off-shore radar towers and oildrilling rigs and platforms, once fouled, are much more prone to becomecorroded or rotted. For this reason, an extensive and costly program ofprophylaxis and maintenance is followed in an effort to cut down theeven more expensive deleterious effects of the marine fouling.

The most common method of reducing the amount of the shell-likeencrustation built up by the lower forms of marine life such asbarnacles or other lower marine creatures is to paint the material to beprotected with a special copper oxide based paint. However, the amountof copper oxide required adversely affects the physical characteristicsof the paint and its normal life is reduced. In addition, the presenceof a large quantity of copper oxide on a metal boat or ship willeventually create an electrolytic cell which greatly accelerates thetendency toward corrosion. To prevent this electrolytic corrosion thesurface must first be covered by an additional and expensive coat ofpaint to insulate the copper oxide from the hull. But even when soprotected, the hull of any ship or boat must be routinely scraped toremove the fouled surface which forms albeit more slowly. Obviously too,this is expensive, since in addition to requiring costly andtime-consuming dry-docking, scraping and repainting, the ship is removedfrom profitable use. For the above reasons, it can readily be seen thatthe discovery of compounds possessing anti-marine fouling properties P OCC110(0H) at low concentrations is of extreme commercial importance.While the mechanism by which the compounds of this invention retardmarine fouling is not understood, it has been found that these compoundsfunction well at economically feasible concentrations, are non-corrosivein themselves and being readily compatible with the oils, bases andadjuvants commonly used in paints can readily be formulated in marinepaints and coatings in general.

While the compounds of this invention are advantageous as anti-marinefouling agents, they possess in addition other important advantages. Forexample, the novel compositions of this invention are useful as fireretardants and mildew retardants whenformulated in organi dcoatiugs .v-,

liiaddition, these compositions may be used as intermediates in thepreparation of other anti-fouling compositions. Thus, when an ester C Cl(OI-I)PO(OR (0R is heated with one to three moles of an amide RRNH,phosphonamides of the type are produced. These compounds also haveactivity as marine anti-fouling substances and as biotoxicants.

A related but ancillary advantage that the compounds of this inventionpossess generally is that they are valuable intermediates for organicsynthesis, in that the reactive and free OH group may be furtheracylated by acylating agents such as acid chlorides and alkylated byalkylating agents such as alkyl sulfates to make compounds of the type CCI (OR )PO(OR )(OR where R is alkyl or acyl.

The need for effective fire-retardant resins, films, coatings, foams andelastomers has become especially acute with the increasing dependenceupon resins and polymeric substances as construction materials. Forexample, today a wide variety of articles of commerce such as houses,boats, aircraft, automobiles, household appliances (as well as theirparts or coating), formerly manufactured out of fire resistant materialssuch as metal or stone are now produced from resins or resin-containinglaminates. Yet all of these items to be acceptable must befire-retardant or resistant. While it has been known for some time thatvarious chlorine and phosphoruscontaining compounds can impart fireretardancy to resins, the problem has been to find compositions whichwhile reducing flammability, do not adversely aifect the desirableproperties of the resin, its strength, stability to heat, light,moisture and oxygen, as well as its aesthetic appearance. ldeally, afire-retardant additive must not only have the positive attribute ofincreasing fire-retardance, being economical and stable, but inaddition, it must not tend to migrate, diffuse, segregate nor contributeto instability toward light, moisture, oxygen nor plasticize the resinunduly. Because of these rather stringent requirements, fewfire-retardant additives have been entirely satisfactory.

However, the applicants have found unexpectedly that their novelphosphonate esters combine all of the characteristics of a desirablefire-retardant additive that is low cost, good fire-retardance, goodchemical and physical stability and low vapor pressure and plasticizingcharacter and generally good compatibility with resin components. Thiscombination of desirable characteristics allows the phosphonate esterproducts of this invention to be incorporated into resins ofdiversecharacteristics and formulations including but not limited topolystyrenes, polyacrylates and methacrylates, polyolefins, dienepolymers, asphalts, indenecoumarone resins, petroleum resins, vinylresins, polyester resins, phenolic resins, epoxy resins, polycarbonateresins, urea and melamine resins, natural gum resins and resinouscoatings.

The fire-retardant additives of this invention may be used in differentforms of resins including moldings, castings, laminates, films, foams,extrusions, coatings and filaments among others.

In certain instances, where R or R is unsaturated (e.g., allyl), theinventive phosphonate resins may be co-polymerized with monomers such asvinyl monomers, to make flame-retardant co-polymers.

The compounds of this invention range from liquids to high meltingsolids, depending on the groups R and R and may be made by the followingreaction:

001 031 oak-001 0:0 HPO(OR1)(ORZ) 0% 01 or omonuomrwnmom) where R and Rare defined as heretofore. The preparation and structure of theperchloropentacyclodecanone has been described by McBee et al., J. Am.Chem. Soc., 78 1511 (1956). j

Thus, suitable reactants of the type HOP(OR (0R are phosphorous acid,and mono and di esters of phosphorus acid. Suitable esters are ingeneral any mono and di ester of phosphorous acid. Examples of theseesters include but are not limited to methyl phosphite, dimethylphosphite, diethyl phosphite, dipropylphosphite, dibutylphosphite,dihexyl phosphite, dioctyl phosphite, didecyl phosphite, didodecylphosphite, distearyl phosphite, dioleyl phosphite, dilinoleylphosph-ite, methyl linoleyl phosphite, di(2-chloroethyl)phosphite,(ii-(2- chloropropyl phosphite), bis-(2,3-dibromopropyl) phosphite,diallyl phosphite, dimethallyl phosphite, di(ethoxyethyl) phosphite,di(carbityl)phosphite, di(cyclohexyl) phosphite, dibenzyl phosphite,diphenyl phosphite, phosphite, dicresyl phosphite,di(chlorinated-phenyl)phosphite, di(alkylated-phenyl) phosphite,di(tetrahydrofurfuryl) phosphite, 1,2-bis(phenylphosphito)ethane, 1,2-bis(2-chloroethyl phosphito) ethane and such cyclic phosphites asethylene phosphite, trimethylene phosphite, tetramethylene phosphite,pentamethylene phosphite, hexamethylene phosphite, butenediol phosphite,and such complex phosphites as to name a few. The esters of phosphorousacid are preferred over the free phosphorous acid because of greaterstability and compatibility of the products with resins.

The process of the invention is conducted by admixing the two reactants,preferably in 1:1 molar ratio of C Cl O to HPO(OR )(OR or with a smallexcess of the phosphite, and warming if necessary to complete thereaction. The reaction can be carried out even below zero degreescentigrade with most phosphites but proceeds more rapidly at highertemperatures up to the boiling point or decomposition point of thephosphite. However, it is not necessary to exceed one hundred and fiftydegrees centigrade for even the more sluggishly-reacting phosphites.Thus, the preferred range is zero degrees to one hundred and fiftydegrees centigrade. Where the phosphite is a liquid at the desiredreaction temperature no solvent is phenyl mols), of free S0 necessary,but in order to facilitate heat transfer and mixing, the use of asolvent is convenient and preferred. Any solvent inert to the tworeactants may be used; suitable solvents are for example aromatichydrocarbons such as toluene, chlorinated hydrocarbons such asperchloroethylene, ketones such as acetone, esters such as butylacetate, ethers such as diisopropyl ether, and N,N- dialkyl amides suchas dimethylformamide.

Isolation of the product is done either by filtration when it isinsoluble in the chosen solvent, or by evaporation of the solvent.Distillation as a means of'purification is not generally practicalbecause of the compositions extremely high boiling points. Purification,where desired, is generally done by recrystallization from a solvent.

The diesters of the invention may be saponified to monoesters or to theacid or salts thereof by heating with water or with a base such ascaustic soda or potash in alcohol. They may also be converted to novelamides by treatment with ammonia or amines. Such amides share many ofthe useful properties of the esters.

Example 1 The ketone C Cl O is prepared as follows: A charge of onehundred and eighty-eight parts (.69 mol), of hexachlorocyclopentadieneis cooled to five to ten degrees centigrade and to the agitated chargeis added gradually nine hundred and forty parts of sixty percent oleum(containing five hundred and sixty-five parts (7.1 After addition of allthe oleum, which requires about one hour, the mixture, whose temperaturerises progressively to about seventy degrees centigrade, is added slowlyto a large volume (five thousand parts), of water to dilute the acid.The crude precipitates immediately upon contact of the charge with thewater, as a white solid. The product is filtered from the spent acid,stirred three times with fresh water, and filtered after each waterwash, to remove most of the sulfuric acid. The product is furtherpurified by dissolving it in five hundred parts of ninety-five percentethanol, reprecipitating by the addition of five hundred parts water,filtering and drying. The hydrated ketone is dehydrated by refluxingwith xylene in a flask fitted with a Dean-Stark trap until no furtherwater is evolved, then stripping the xylene ofi". The infra-red spectrumconfirmed the identity of the product.

A mixture of 18.8 parts of dimethylphosphite, 49.1 parts of the ketone CCl O (prepared as described above), and two hundred parts of xylene areheated at Example 2 A mixture of 45.5 parts of di-n-butyl phosphite,49.1 parts of the ketone C Cl O, and two hundred parts of xylene isheated at ninety degrees for nineteen hours. The solvent is stripped offunder vacuum and the residue washed with hexane, leaving ahexane-insoluble colorless solid, melting point one hundred and fiftydegrees.

Analysis.-Calcd. for C H O PCl Cl, 49.8 percent; P, 4.3 percent. Found:Cl, 50.6 percent; P, 4.7 percent.

Example 3 A mixture of eighty-four parts of dilauryl phosphite,ninety-eight parts of the ketone C Cl O and four hundred parts of Xyleneis heated for nineteen hours at one hundred degrees. The solvent is thenstripped oil? under enoaeoa vacuum at one hundred degrees leaving aquantitative yield of a nearly colorless oil, whose infrared spectrumshows the absence of the carbonyl group and the presence of the P O andOH groups.

Analysis.Calcd. for C34H5104PC110: C1, percent; P, 3.4 percent. Found:CI, 38.2 percent; P, 2.8 percent.

Example 4 A mixture of 46.8 parts of diphenyl phosphite, 49.1 parts ofthe ketone C Cl O, and two hundred parts of Found: Cl, 48.9 percent.

Cit

Example 6 A mixture of forty parts of cyclic phosphite of commercialhexylene glycol, 49.1 parts of the ketone C Cl O, and two hundred partsof benzene is refluxed for one day, then evaporated under reducedpressure to remove the A substantially theoretical 0 toluene is heatedat ninety degrees for forty-three hours, 1 benzene and excess phosphite.then the solvent evaporated by application of vacuum. yield of an almostcolorless viscous syrup is obtained The residue is recrystallized fromcarbon tetrachloride to which upon standing partially solidifies. obtainthirty-eight parts of colorless solid, melting point Analysis.-Calcd.for C H O PCl Cl, 54.3 percent; two hundred and thirty-nine degreescentigrade. 15 P, 4.74 percent. Found: Cl, 53.9, percent; P, 4.8percent.

Analysis.-Calcd. for C H O PCl CI, 48.8 percent. Example 7 E l 5 The CCl O ketone of Example 1 is reacted with the xamp e followingphosphonates using analogous synthetic tech- A mixture of 17.8 parts ofdiallyl phosphate, 49.1 parts 20 niques, equipment and the like as setforth in detail in of the ketone C Cl Qand two hundred parts ofchlorobenzene are heated for two hours at ninety degrees, then thesolvent stripped ofi by applying vacuum and the residue recrystallizedfrom Xylene to obtain sixty-three Examples 1-6. The left hand columngives the compound formed and the right hand column gives the otherreactant used. The hydroxy-phosphonate structure was confined byinfrared spectra.

C10C110(OH)PO(OOH2CHgOH)g HPO(OCH2CHzOH)z onion, onto-n2 C C11o(OH)POOCH on, n20 OCH on,

k onion, 2 onion, 2

onion: onion.

C 0Cl1o(OH)PO OCH on; HIO OOH on.

onolonz 2 oncwni g Compound D erived from- HPO C NOD, CH3),

B r w r CC110(OH)PO OCH2CH CH2 HPO OCHzCH CH2 0 a O 2 (311-4511(|[]H-(|TH CmC11o(OH)PO OCHzC CH HPO OOHzC CH O OCHz O OCH: H/ II/OmG1w(oH)P HP\ 0 OCH: 0 OCH: H/ H/ C oClw(OH)P\ 0H, HP\ /OH 0 CH 0 on;(I) OCHQCH: (3/0 CHzCHn C1uC11u(OH)P HP OCHqCH, OCHZOHQ o OCHiCHzCHz 00011101120112 10Cho(OH)P HP 0 01110112011, 0 01120112011, 0 0-CH;CH 0O-CH2-CH ll/ ll/ C1oCli0( H)P HP\ O-CHz-GH O-CH2CH OCH1OH-C 01 oornon-o01 0 01 OH P 0 HP 0 0011 n 0012 u OGHzCH CO1 OCHa H I 001 0 O\ 0 ll I] CoClw(OH)P HP 0 0 fi/O CH2 CHzOH 3 OCH: OHZOH C10Cl1o(OH) P\ C\ HP\ /C\ OC CzH5 O CH: 01H;

0 OCH, C1120 dellVEd from H mCIM IDP Y 0 POC Cho(OH) g \OHQO HP 000m o-oPmoouno derived from Example 8.-(Fire retardant-y test) i E E Thetesting Was carried out by the method of ASTM HP 0 HC1nC11o( TestD635-56T, which is conducted briefly as follows: A gfi \(3112() test barfive inches by one-half inch by one-eighth of an inch, composed ofpolystyrene containing fifteen percent of the product of Example 1 or 4,is supported horizontally and exposed for thirty seconds to the directflame of a Bunsen burner. The resin bars containing the additives wereself-extinguishing.

Example A similar test to the foregoing was done with polypropylene ofwhich it is more diflicult to repress the flammability. At thirtypercent loading with the products of ll 1 Examples 1-5, burning rates of0.1 to 0.2 inch per minute are observed. In comparison, thirty percentof the ketone C Cl O in polypropylene gives a burning rate of 0.64 inchper minute, and polypropylene without additive gives a burning rate ofone to 1.5 inches per minute.

Example 10.A formulation of marine paint having antifouling propertiesThe following ingredients are blended and ground together in a ballmill. Six different formulations are made up differing only by thephosphonate ester product used.

Ingredient: Pounds per 100 gallons Gum rosin, grade WW 277 Blown fishoil 118 Zinc stearate 18 A product from Examples 1-6 197 Zinc oxide 161Magnesium silicate 56 Solvent naphtha, approx. 241 Lampblack 1 Volumeadjusted to 100 gal. by addition of naphtha.

Example ]1.Anther formulation of a marine paint having anti-foulingproperties The following ingredients are blended and ground together ina ball mill. Six different formulations are made up differing only inthe phosphonate ester used.

Pounds per Ingredient: 100 gallons Rosin 311 \F Hydrogenated methylabietate 115.5

Coal tar naphtha 92.4

Mineral spirits (paint thinner) (approx) 103.7

Diatomaceous silica 103.7 A product from Examples 1-6 311 Lampblack 1.0

Volume adjusted to 100 gallons by addition of mineral spirits.

Example 12.Additional formulations of marine paints having anti-foulingproperties The following ingredients are blended together in theindicated proportions in a ball mill using a product obtained from thepreparations of Examples 1-6. Thus, six formulations dififering only inactive ingredient are prepared.

Pounds per Ingredient: 100 gallons Rosin 265 Coal tar 80 Talc 80 Pineoil 42 C Cl (Ol-l) (PO(OCH from Example 1 200 High flash naphtha 135)Mineral spirits 1 Make up to volume.

Example 13.Additi0nal formulations of marine paints having anti-foulingproperties The following ingredients are blended together in the denotedproportions in a roller mill. Six formulations are prepared differingonly in the C Cl ,(OH) phosphonate ester used.

JAM Example 14.Testing of paint formulations of the preceding examplesfor anti-fouling properties The formulations disclosed in the precedingexamples are painted on steel test panels, allowed to dry and immersedin sea water at a sub-tropical location. At the same time otheridentical panels are painted with control test formulations identicalwith these paint preparations except that the phosphonate derivativesare omitted from the formulation. These test panel are immersed in thesame subtropical sea water. After one month, both the control testpanels and the panels containing the active component are examined andcompared. It is found that the control panels are heavily crusted with amixed population of barnacles and other marine organisms, while thepanels containing the active anti-marine fouling' component were notfouled to any serious degree.

Example 15.-Copolymerization of product of Example 5 The product ofExample 5 was mixed with ten parts by weight of styrene monomer and 0.1percent by weight of benzoyl peroxide was added. The mixture was heatedto one hundred degrees Centigrade until polymerization occurred.

The resulting polymer was selfextinguishing when ignited.

wherein R and R are independently selected from the group consisting ofhydrogen; alkyl of up to 18 carbon atoms; substituted alkyl of up to 18carbon atoms, in which the substituents are selected from the groupconsisting of halogen, alkoxy, aryloxy, nitro, alkylmercapto,arylmercapto and alkenyl; aryl; substituted aryl, in which thesubstituents are selected from the group consisting of halogen, alkoxy,aryloxy, nitro, alkylmercapto, arylmercapto},

substituents are selected from the group consisting of halowherein R andR are conjoined; substituted alkylene of up to 18 carbon atoms, in whichthe substituents are selected from the group consisting of halogen,alkoxy, aryloxy, nitro, alkylmercapto, arylmercapto, alkyl and alkenyl;phenylene, wherein R and R are conjoined through the phenyl group; andsubstituted phenylene of 6 to 18 carbon atoms, in which the substituentsare selected from the group consisting of halogen, alkoxy, aryloxy,nitro, alkylmercapto, arylmercapto, alkyl and alkenyl, whereinabove arylis monocarbocyclic.

2. A compound according to claim 1 in which R and R are alkyl groups ofup to 18 carbon atoms.

3. A compound according to claim 1 in which R and R 4are alkenyl groupsof up to 18 carbon atoms.

m C I H H O i H r 0 w 4 w OHPIO O P O 4 H H 1 G O m c c m m m 1 1FTCJILTC m c LTm m+ is m c m ml||olfl||clm m c c m O 1\ /1 0 0 m m 2 7.8 9 W 5 M M w 3 M w m C O P O H \CIO GIG 3 m L o m 1 1 1 c o C C 1 1 1 v010 C C T C m m c c m G 1\ /l C 0 References Cited by the ExaminerUNITED STATES PATENTS 2,616,928 11/52 Gilbert et a1. 260586 NICHOLAS S.RIZZO, Primary Examiner. 3O WALTER A. MODANCE, IRVING MARCUS,

Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,202,692 August 24, 1965 Edward D. Weil et al corrected below.

Column 2, lines 55 to 58, t

he formula should appear as shown below instead of as in the patent:

CH CH same column 2, lines 64 and 65, for

C10C110(0H)P0(0C H5)OCH CH OP(OC H )C C110(0H) read C C1 (OH) PO(OC H)OCH CH OPO(OC H C Cl (0H] same column 2, lines 66 to 68, for

read

column 5, lines 10 to 17, the formula should appear as shown belowinstead of as in the patent:

ccgl ccl i z C=O+HPO(ORL) (0R CCl CCl cm I "c1 2 o p I CCl 0 I I/ CCl CC1 (0H) (0R (0R2) column 8, line 24, for "confined" read confirmedcolumns 7 and 8, in the table, under the heading "Derived from-", thetwenty-third formula, for "HPO(OCH CH OC Hr) read HP0(OCH CH OC H sametable, under the heading "Compound", the last formula should appear asshown below instead of as in the patent:

C Cl (OH) -Po 0Q 1-5 2 columns 9 and 10,3, in the table, under theheading "Compound", the second formula should appear as shown belowinstead of as in the patent:

C Cl (OH)PO 0Q same columns 9 and 10, in the table, under the heading"Compound", the thirteenth formula should appear as shown below insteadof as in the patent:

ill/0C? /CH OH C Cl [0H)P C OCH C H column 9, lines 64 to 66, theformula should appear as shown below instead of as in the patent:

OCH CH 0 Fv OCH CH O same column 9, lines 68 and 69, the formula shouldappear as shown below instead of as in the patent:

POC Cl (OH) C C1 (OH)P(OC H )OCH CH OPC C1 (OH) (OC H same column 9,lines 74 to 76, the formula should appear as shown below instead of asin the patent:

column 12, line 49, for "substituents are selected from the groupconsisting of halo-" read alkyl and alkenyl; alkylene of up to 18 carbonatoms,

Signed and sealed this 29th day of November 1966.

(SEAL) Attest:

ERNEST W. SWIDER EDWARD BRENNER Attesting Officer Commissioner ofPatents

